CN116507415A - Catalyst systems and processes using SSZ-91 and SSZ-95 - Google Patents
Catalyst systems and processes using SSZ-91 and SSZ-95 Download PDFInfo
- Publication number
- CN116507415A CN116507415A CN202180081273.1A CN202180081273A CN116507415A CN 116507415 A CN116507415 A CN 116507415A CN 202180081273 A CN202180081273 A CN 202180081273A CN 116507415 A CN116507415 A CN 116507415A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- catalyst composition
- ssz
- product
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 57
- 239000002199 base oil Substances 0.000 claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims description 94
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000010724 circulating oil Substances 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000010913 used oil Substances 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052800 carbon group element Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910021476 group 6 element Inorganic materials 0.000 description 2
- 229910021474 group 7 element Inorganic materials 0.000 description 2
- 229910021472 group 8 element Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 nitrogen containing hydrocarbon Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7446—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7461—MRE-type, e.g. ZSM-48
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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Abstract
An improved hydroisomerization catalyst system and process for preparing a base oil product using a combined catalyst system comprising an SSZ-91 molecular sieve and an SSZ-95 molecular sieve. The catalyst systems and processes generally involve the use of a catalyst comprising an SSZ-91 molecular sieve and a separate catalyst comprising an SSZ-95 molecular sieve to produce a dewaxed base oil product by sequentially contacting the catalyst with a hydrocarbon feedstock. The catalyst systems and processes provide improved base oil yields as well as other beneficial base oil properties.
Description
Cross Reference to Related Applications
The present application claims priority from U.S. patent application Ser. No. 17/095,337, filed 11/2020, the disclosure of which is incorporated herein in its entirety.
Technical Field
A hydroisomerization catalyst system and process for producing a base oil from a hydrocarbon feedstock using a catalyst comprising an SSZ-91 molecular sieve and an SSZ-95 molecular sieve.
Background
Hydroisomerization catalytic dewaxing processes for producing base oils from hydrocarbon feedstock involve introducing the feedstock in the presence of hydrogen into a reactor containing a dewaxing catalyst system. Within the reactor, the feed is contacted with a hydroisomerization catalyst under hydroisomerization dewaxing conditions to provide an isomerized stream. Hydroisomerization removes aromatics and residual nitrogen and sulfur and isomerizes normal paraffins to improve cold flow properties. The isomerized stream may be further contacted with a hydrofinishing catalyst in a second reactor to remove traces of any aromatics, olefins, improve color, etc. from the base oil product. The hydrofinishing unit may comprise a hydrofinishing catalyst comprising an alumina support and a noble metal, typically palladium, or a combination of platinum and palladium.
Challenges generally faced in typical hydroisomerization catalytic dewaxing processes include, among other things, providing one or more products that meet relevant product specifications (such as cloud point, pour point, viscosity, and/or viscosity index limits of the product (s)) while also maintaining good product yields. In addition, further upgrades may be used, for example during hydrofinishing, to further improve product quality, for example to achieve color and oxidation stability by saturating the aromatic hydrocarbon to reduce the aromatic hydrocarbon content. However, the presence of residual organic sulfur and nitrogen from upstream hydrotreating and hydrocracking processes can have a significant impact on downstream processes and final base oil product quality.
Dewaxing of linear paraffins involves many hydroconversion reactions including hydroisomerization, branched redistribution, and secondary hydroisomerization. The continuous hydroisomerization reaction results in an increase in the degree of branching with a concomitant redistribution of the branches. Increased branching generally increases the likelihood of chain cracking, resulting in greater fuel yield, and loss of base oil/lube yield. Thus, minimizing such reactions (including the formation of hydroisomerization transition species) can result in increased base oil/lube yield.
Thus, there is a need for a more robust catalyst system for base oil/lube oil production to isomerize wax molecules and provide increased base oil/lube oil yield by reducing undesirable cracking and hydroisomerization reactions. Thus, there is a continuing need for catalysts, catalyst systems, and processes for producing base oil/lube oil products while also providing good base oil/lube oil product yields.
Disclosure of Invention
The present invention relates to a hydroisomerization catalyst system and process for converting a waxy hydrocarbon feedstock into higher products, including base oils or lubricating oils, generally having increased yields of base oil products. The catalyst system and process uses a catalyst system comprising a first catalyst composition comprising an SSZ-91 molecular sieve and a second catalyst composition comprising an SSZ-95 molecular sieve. The first catalyst composition and the second catalyst composition are arranged such that the hydrocarbon feedstock can be contacted sequentially with the first catalyst composition or the second catalyst composition to provide a first stage product, followed by contacting the first stage product with the other catalyst composition to provide a second stage product. The hydroisomerization process converts the aliphatic unbranched paraffins (normal paraffins) to isoparaffins and cyclic species, thereby lowering the pour and cloud points of the base oil product compared to the feedstock. It has been found that the catalyst system formed from the combination of SSZ-91 and SSZ-95 advantageously provides a base oil product having an increased base oil/lube oil product yield as compared to a base oil product produced using the SSZ-91 catalyst or the SSZ-95 catalyst itself.
In one aspect, the present invention relates to a hydroisomerization catalyst system and process that can be used to produce dewaxed products, including base oils, particularly one or more product grades of base oil products, by hydroprocessing a suitable hydrocarbon feed stream. Although not necessarily limited thereto, it is an object of the present invention to provide improved base oil product yields while also providing other beneficial base oil product characteristics.
The first catalyst composition generally comprises an SSZ-91 molecular sieve and the second catalyst composition generally comprises an SSZ-95 molecular sieve. Each catalyst composition may further comprise a matrix material and at least one modifier selected from groups 6 to 10 and group 14 of the periodic table of elements. The modifier may also comprise a metal of group 2 of the periodic table of elements.
Hydroisomerization processes generally comprise contacting a hydrocarbon feedstock with a hydroisomerization catalyst system under hydroisomerization conditions to produce a base oil product or product stream. The feedstock may first be contacted with a first catalyst composition or a second catalyst composition to provide a first stage product, and then the first stage product is contacted with the other catalyst composition (i.e., the corresponding second catalyst composition or first catalyst composition) to provide a second stage product. The second stage product may itself be a base oil product or may be used to prepare a base oil product. For example, in some embodiments, the process can provide a base oil product having a viscosity index of at least about 109 and/or a pour point of no greater than about-10 ℃ or-13 ℃.
Detailed Description
Although illustrative embodiments of one or more aspects are provided herein, the disclosed processes can be implemented using a number of techniques. The disclosure is not limited to the illustrative or particular embodiments, drawings, and techniques illustrated herein (including any exemplary designs and embodiments illustrated and described herein), and may be modified within the scope of the appended claims along with their full scope of equivalents.
Unless otherwise indicated, the following terms, terms and definitions apply to the present disclosure. If a term is used in this disclosure, but not specifically defined herein, a definition from the IUPAC chemical terminology assembler, version 2 (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or make any claim applying the definition ambiguous or infeasible. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, it should be understood that the definition or usage provided herein applies.
"API gravity" refers to the specific gravity of a petroleum feedstock or product relative to water, as determined by ASTM D4052-11.
"viscosity index" (VI) means the temperature dependence of the lubricant, as determined by ASTM D2270-10 (E2011).
"vacuum gas oil" (VGO) is a by-product of crude oil vacuum distillation that can be sent to a hydroprocessing unit or to aromatics extraction for upgrading to base oil. VGO typically comprises hydrocarbons having a boiling range distribution between 343 ℃ (649 DEG F) and 593 ℃ (1100 DEG F) at 0.101 MPa.
When used in conjunction with an oil feedstock, "treated", "upgraded (upgrade, upgrading)" and "upgraded" describe a feedstock that is or has been subjected to hydroprocessing, or a resulting material or crude product having a reduction in feedstock molecular weight, a reduction in feedstock boiling point range, a reduction in asphaltene concentration, a reduction in hydrocarbon radical concentration, and/or a reduction in the amount of impurities such as sulfur, nitrogen, oxygen, halides, and metals.
"Hydroprocessing" refers to a process in which a carbonaceous feedstock is contacted with hydrogen and a catalyst at elevated temperature and pressure in order to remove undesirable impurities and/or convert the feedstock into the desired product. Examples of hydroprocessing processes include hydrocracking, hydrotreating, catalytic dewaxing, and hydrofinishing.
"hydrocracking" refers to processes in which hydrogenation and dehydrogenation are accompanied by cracking/fragmentation of hydrocarbons, such as processes that convert heavier hydrocarbons to lighter hydrocarbons, or aromatics and/or cyclic alkanes (naphthenes) to acyclic branched alkanes.
"hydrotreating" refers to a process that converts a sulfur and/or nitrogen containing hydrocarbon feed into hydrocarbon products having reduced sulfur and/or nitrogen content (typically in combination with hydrocracking) and produces hydrogen sulfide and/or ammonia (respectively) as byproducts. Such processes or steps performed in the presence of hydrogen include hydrodesulfurization, hydrodenitrogenation, hydrodemetallization and/or hydrodearomatization of hydrocarbon feedstock components (e.g., impurities), and/or for the hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrotreatment and the reaction conditions, the products of the hydrotreatment process can have, for example, improved viscosity, viscosity index, saturates content, low temperature properties, volatility, and depolarization. The terms "guard layer" and "guard bed" are synonymously and interchangeably used herein to refer to a hydrotreating catalyst or a hydrotreating catalyst layer. The protective layer may be a component of a catalyst system for dewaxing hydrocarbons and may be disposed upstream of at least one hydroisomerization catalyst.
"catalytic dewaxing" or hydroisomerization refers to a process that isomerizes normal paraffins to their more branched counterparts by contact with a catalyst in the presence of hydrogen.
"hydrofinishing" refers to a process that aims to improve the oxidation stability, UV stability and appearance of hydrofinished products by removing traces of aromatics, olefins, color bodies and solvents. UV stability refers to the stability of the hydrocarbons tested upon exposure to UV light and oxygen. Instability is indicated when visible precipitates are formed, often appearing like Hoc or cloudy, or when darker colors are produced after exposure to ultraviolet light and air. General descriptions of hydrofinishing can be found in U.S. Pat. nos. 3,852,207 and 4,673,487.
The term "Hydrogen" refers to Hydrogen itself, and/or one or more compounds that provide a source of Hydrogen.
"cut point" refers to the temperature on the true boiling point (t beta pi) curve when a predetermined degree of separation is reached.
"pour point" refers to the temperature at which the oil begins to flow under controlled conditions. Pour point may be determined by, for example, ASTM D5950.
"cloud point" refers to the temperature at which a lubricating base oil sample begins to develop haze as the oil cools under specific specified conditions. The cloud point of the lubricant base oil is complementary to its pour point. Cloud point can be determined by, for example, ASTM D5773.
"TBP" means the boiling point of a hydrocarbon-containing feed or product as determined by simulated distillation (SimDist) according to ASTM D2887-13.
"Hydrocarbon", "hydrocarbon" and similar terms refer to compounds containing only carbon and hydrogen atoms. Other identifiers may be used to indicate the presence of a particular group, if any, in the hydrocarbon (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).
The term "periodic table" refers to the version of the IUPAC periodic table at 6, 22 days of 2007, and the numbering scheme of the periodic table groups is as described in chem. "group 2" refers to IUPAC group 2 elements, such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and combinations thereof in any of elemental, compound or ionic forms. "group 6" means an IUPAC group 6 element such as chromium (Cr), molybdenum (Mo), and tungsten (W). "group 7" refers to IUPAC group 7 elements, such as manganese (Mn), rhenium (Re), and combinations thereof, in any of elemental, compound, or ionic form. "group 8" refers to an IUPAC group 8 element, such as iron (Fe), ruthenium (Ru), osmium (Os) in any of elemental, compound, or ionic forms, and combinations thereof. "group 9" refers to IUPAC group 9 elements, such as cobalt (Co), rhodium (Rh), iridium (Ir), and combinations thereof, in any of elemental, compound, or ionic form. "group 10" refers to IUPAC group 10 elements, such as nickel (Ni), palladium (Pd), platinum (Pt), and combinations thereof, in any of elemental, compound, or ionic forms. "group 14" refers to IUPAC group 14 elements, such as germanium (Ge), tin (Sn), lead (Pb), and combinations thereof, in any of elemental, compound, or ionic forms.
The term "support", particularly as used in the term "catalyst support", refers to a conventional material, typically a solid having a high surface area, to which the catalyst material is attached. The support material may be inert or participate in the catalytic reaction and may be porous or non-porous. Typical catalyst supports include various carbons, aluminas, silicas, and silica-aluminas, such as amorphous silica aluminates, zeolites, alumina-boria, silica-alumina-magnesia, silica-alumina-titania, and materials obtained by adding other zeolites and other composite oxides to the foregoing materials.
"molecular sieve" refers to a material having pores of uniform molecular size within the framework structure such that, depending on the type of molecular sieve, only certain molecules may enter the pore structure of the molecular sieve, while other molecules are excluded, for example, due to molecular size and/or reactivity. The terms "molecular sieve" and "zeolite" are synonymous and include (a) intermediates and (b) final or target molecular sieves as well as molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary modification). Secondary synthesis techniques allow synthesis of target materials from intermediate materials by heteroatom lattice substitution or other techniques. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatom lattice substitution of Al for B. Such techniques are known, for example, as described in U.S. patent No. 6,790,433. Zeolites, crystalline aluminum phosphate and crystalline silicoaluminophosphate are representative examples of molecular sieves.
In this disclosure, although the compositions and methods or processes are generally described in terms of "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components or steps, unless otherwise indicated.
The terms "a," "an," and "the" are intended to include alternatives, e.g., at least one. For example, the disclosure of "transition metal" or "alkali metal" is intended to cover one transition metal or alkali metal, or a mixture or combination of more than one transition metal or alkali metal, unless otherwise indicated.
All numbers in the detailed description and claims herein are modified by the value indicated as "about" or "approximately" and take into account experimental errors and variations as would be expected by one of ordinary skill in the art.
In one aspect, the invention is a hydroisomerization catalyst system useful in the preparation of dewaxed products including base oil/lubricant oils comprising a first catalyst composition comprising an SSZ-91 molecular sieve and a second catalyst composition comprising an SSZ-95 molecular sieve. The first catalyst composition and the second catalyst composition are arranged such that the hydrocarbon feedstock can be contacted sequentially with the first catalyst composition or the second catalyst composition to provide a first stage product, followed by contacting the first stage product with the other catalyst composition to provide a second stage product. The first catalyst composition generally comprises an SSZ-91 molecular sieve and the second catalyst composition generally comprises an SSZ-95 molecular sieve. Each catalyst composition may further comprise a matrix material and at least one modifier selected from groups 6 to 10 and group 14 of the periodic table of elements. The modifier may also comprise a metal of group 2 of the periodic table of elements.
In a further aspect, the present invention relates to a hydroisomerization process useful for producing dewaxed products including base oils, the process comprising contacting a hydrocarbon feedstock with a hydroisomerization catalyst system under hydroisomerization conditions to produce a base oil product or product stream. The feedstock may first be contacted with a first catalyst composition or a second catalyst composition to provide a first stage product, and then the first stage product is contacted with the other catalyst composition (i.e., the corresponding second catalyst composition or first catalyst composition) to provide a second stage product. The second stage product may itself be a base oil product or may be used to prepare a base oil product.
SSZ-91 molecular sieves used in hydroisomerization catalyst systems and processes are described, for example, in U.S. patent nos. 9,802,830, 9,920,260, 10,618,816 and WO 2017/034823. SSZ-91 molecular sieves typically comprise ZSM-48 type zeolite material having at least 70% of the polytype 6 of the total ZSM-48 type material; type EUO phase in an amount between 0% and 3.5% by weight; and a polycrystalline aggregate morphology comprising crystallites having an average aspect ratio between 1 and 8. The SSZ-91 molecular sieve can have a silica to alumina mole ratio in the range of 40 to 220 or 50 to 220 or 40 to 200. In some cases, the SSZ-91 molecular sieve may have at least 70% polytype 6 of the total ZSM-48 type material; an EUO-type phase in an amount of 0 wt% to 3.5 wt%; and a polycrystalline aggregate morphology comprising crystallites having an average aspect ratio of between 1 and 8. In some cases, the SSZ-91 material consists of at least 90% of polytype 6 of the total ZSM-48-type material present in the product. The structure of polytype 6 has been given the framework code MRE by the structural committee of the international zeolite association. The terms "MRE type molecular sieve" and "EUO type molecular sieve" include all molecular sieves specified in the framework of the international zeolite association and their isotypes, as described in Atlas of Zeolite Framework Types, editor Ch.Baerlocher, L.B.Mccusker and d.h. olson, elsevier, revision 6, 2007 and the zeolite structure database on the international zeolite association website (http:// www.iza-online.org).
The foregoing noted patent provides additional details regarding SSZ-91 molecular sieves, methods of making the same, and catalysts formed therefrom.
SSZ-95 molecular sieves used in hydroisomerization catalyst systems and processes are described, for example, in U.S. Pat. Nos. 9,573,124, 10052619, 10272422 and WO 2015/179228. SSZ-95 molecular sieves are typically MTT framework molecular sieves having a silica to alumina mole ratio of 20 to 70, a total micropore volume of between 0.005 and 0.02 cc/g; and H-D exchangeable acid site densities of up to 50% relative to SSZ-32.
The molecular sieve of each of the first and second catalyst compositions is typically combined with a matrix material to form a first base material and a second base material, respectively. The base material may be formed into a base extrudate, for example, by: the molecular sieve is combined with the matrix material, the mixture is extruded to form a shaped extrudate, and the extrudate is then dried and calcined. Each of the first and second catalyst compositions typically further comprises at least one modifier selected from groups 6 to 10 and 14 of the periodic table of elements and optionally further comprises a group 2 metal. The modifier may be added by using an impregnation solution containing a modifier compound.
Suitable matrix materials for one or both of the first catalyst composition and the second catalyst composition include alumina, silica, ceria, titania, tungsten oxide, zirconia, or combinations thereof. In some embodiments, the alumina used in the first catalyst composition and/or the second catalyst composition and the process may also be "high nanopore volume" alumina (abbreviated "HNPV" alumina) as described in U.S. application serial No. 17/095,010 (case No. T-11311) filed 11, 2020, which is incorporated herein by reference. Suitable aluminas are commercially available and include, for example, those from SasolAlumina and->Alumina or +.>Alumina.
Suitable modifiers are selected from groups 6 to 10 and group 14 of the periodic Table of the elements (IUPAC). Suitable group 6 modifiers include group 6 elements such as chromium (Cr), molybdenum (Mo), and tungsten (W) in any of elemental, compound, or ionic form, and combinations thereof. Suitable group 7 modifiers include group 7 elements such as manganese (Mn), rhenium (Re), and combinations thereof in any of elemental, compound, or ionic form. Suitable group 8 modifiers include group 8 elements such as iron (Fe), ruthenium (Ru), osmium (Os) in any of elemental, compound, or ionic forms, and combinations thereof. Suitable group 9 modifiers include group 9 elements such as cobalt (Co), rhodium (Rh), iridium (Ir), and combinations thereof in any of elemental, compound, or ionic form. Suitable group 10 modifiers include group 10 elements such as nickel (Ni), palladium (Pd), platinum (Pt) in any of elemental, compound, or ionic form, and combinations thereof. Suitable group 14 modifiers include group 14 elements such as germanium (Ge), tin (Sn), lead (Pb), and combinations thereof in any of elemental, compound, or ionic form. In addition, optional group 2 modifiers may be present, including group 2 elements, such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof, in any of elemental, compound, or ionic form.
The modifier advantageously comprises one or more group 10 metals. The group 10 metal may be, for example, platinum, palladium, or a combination thereof. In some aspects, platinum is a suitable group 10 metal and another group 6 to 10 and group 14 metal. Although not limited thereto, the group 6 to 10 and group 14 metals may be more narrowly selected from Pt, pd, ni, re, ru, ir, sn or combinations thereof. In combination with Pt as the first metal in the first catalyst composition and/or the second catalyst composition, the optional second metal in the first catalyst composition and/or the second catalyst composition may also be more narrowly selected from group 6 to 10 and group 14 metals, such as Pd, ni, re, ru, ir, sn or combinations thereof. In more specific cases, the catalyst may comprise Pt as a group 10 metal in an amount of 0.01 to 5.0 wt% or 0.01 to 2.0 wt% or 0.1 to 2.0 wt%, more particularly 0.01 to 1.0 wt% or 0.3 to 0.8 wt%. The optional second metal selected from Pd, ni, re, ru, ir, sn as a group 6 to 10 and group 14 metal or a combination thereof may be present in an amount of 0.01 to 5.0 wt% or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt%, more particularly 0.01 to 1.0 wt% and 0.01 to 1.5 wt%.
The metal content in the first and second catalyst compositions can vary within useful ranges, for example, the total modified metal content of the catalyst can be from 0.01 to 5.0 wt.% or from 0.01 to 2.0 wt.% or from 0.1 to 2.0 wt.% (based on total catalyst weight). In some cases, the catalyst composition comprises 0.1-2.0 wt.% Pt as one of the modifying metals and 0.01-1.5 wt.% a second metal selected from groups 6-10 and 14, or 0.3-1.0 wt.% Pt and 0.03-1.0 wt.% second metal, or 0.3-1.0 wt.% Pt and 0.03-0.8 wt.% second metal. In some cases, the ratio of the first group 10 metal to the optional second metal selected from groups 6 to 10 and 14 may be in the range of 5:1 to 1:5, or 3:1 to 1:3, or 1:1 to 1:2, or 5:1 to 2:1, or 5:1 to 3:1, or 1:1 to 1:3, or 1:1 to 1:4. In more specific cases, the first catalyst composition and/or the second catalyst composition comprises from 0.01 wt% to 5.0 wt% of the modifying metal, from 1 wt% to 99 wt% of the matrix material, and from 0.1 wt% to 99 wt% of the SSZ-91 or SSZ-95 molecular sieve.
The base extrudate may be prepared according to any suitable method. For example, the base extrudate of the first catalyst composition and/or the second catalyst composition may be conveniently prepared by mixing the components together and extruding the well-mixed SSZ-91/matrix material and/or SSZ-95/matrix material mixture to form the base extrudate. The extrudate is then dried and calcined, followed by loading any modifiers onto the base extrudate. The modifier may be dispersed onto the base extrudate using a suitable impregnation technique. However, the method of preparing the base extrudate is not intended to be particularly limited depending on the particular process conditions or techniques.
The hydrocarbon feed may generally be selected from a variety of base oil feedstocks, and advantageously comprises a gas oil; vacuum gas oil; long residue (long residue); vacuum residue; atmospheric distillate; a heavy fuel; an oil; waxes and paraffins; used oil; deasphalted residue or crude oil; charges (charges) resulting from thermal or catalytic conversion processes; shale oil; circulating oil; fats, oils and waxes of animal and vegetable origin; petroleum and slack wax; or a combination thereof. The hydrocarbon feed may also comprise a feed hydrocarbon fraction (cut) in the distillation range of 400-1300°f, or 500-1100°f, or 600-1050°f, and/or wherein the hydrocarbon feed has a KV100 (kinematic viscosity at 100 ℃) range of about 3 to 30cSt, or about 3.5 to 15 cSt.
In some cases, the process may be advantageously used for light or heavy neutral base oil feedstocks, such as Vacuum Gas Oil (VGO), as hydrocarbon feeds, wherein SSZ-91 and SSZ-95 catalyst compositions comprise Pt modified metals, or a combination of Pt and another modifier.
The one or more products, or product streams, may be used to produce one or more base oil products, such as producing a multi-grade (multi grade) having a KV100 in the range of about 2 to 30 cSt. In some cases, such base oil products may have a pour point of no more than about-10 ℃ or-13 ℃.
The process and catalyst system may also be combined with additional process steps or system components, for example, the feedstock may be further subjected to hydrotreating conditions with a hydrotreating catalyst prior to contacting the hydrocarbon feedstock with the SSZ-91 catalyst composition or the SSZ-95 catalyst composition, optionally wherein the hydrotreating catalyst comprises a guard layer catalyst comprising a refractory inorganic oxide material comprising about 0.1 wt% to 1 wt% Pt and about 0.2 wt% to 1.5 wt% Pd.
One of the advantages provided by the process and catalyst system of the present invention is that the yield of base oil product produced using a combination of a first catalyst composition and a second catalyst composition based on SSZ-91 and SSZ-95 molecular sieves is improved over the same process using either the SSZ-91 catalyst composition alone or the SSZ-95 catalyst composition alone. For example, the base oil yield when using a combination of first and second SSZ-91 and SSZ-95 catalyst compositions can be significantly increased by at least about 0.5 wt.% or 1.0 wt.% as compared to using only SSZ-91 or SSZ-95 catalyst compositions in the same process.
In practice, hydrodewaxing is mainly used to lower the pour point of the base oil and/or to lower the cloud point of the base oil by removing wax from the base oil. Typically, dewaxing processes wax using catalytic processes, typically upgrading the dewaterer feed prior to dewaxing to increase viscosity index, reduce aromatics and heteroatom content, and reduce the amount of low boiling components in the dewaterer feed. Some dewaxing catalysts accomplish the wax conversion reaction by cracking waxy molecules into lower molecular weight molecules. Other dewaxing processes can convert waxes contained in hydrocarbon feeds to the process by wax isomerization to produce isomerized molecules having a pour point lower than the non-isomerized molecular counterparts. As used herein, isomerization includes hydroisomerization processes that use hydrogen in the isomerization of wax molecules under catalytic hydroisomerization conditions.
Suitable hydrodewaxing conditions will generally depend on the feed used, the catalyst used, the desired yield and the desired base oil properties. Typical conditions include temperatures of 500°f to 775°f (260 ℃ to 413 ℃); a pressure of 15psig to 3000psig (0.10 MPa to 20.68MPa gauge); 0.25hr -1 For 20hr -1 Is a LHSV of (2); and 2000SCF/bbl to 30,000SCF/bbl (356 to 5340 m) 3 H 2 /m 3 Feed) hydrogen to feed ratio. Typically, hydrogen is separated from the product and recycled to the isomerization zone. Typically, the dewaxing process of the present invention is performed in the presence of hydrogen. Typically, the ratio of hydrogen to hydrocarbon may be in the range of about 2000 to about 10,000 standard cubic feet H 2 Barrel hydrocarbon and typically about 2500 to about 5000 standard cubic feet H 2 In the range of barrel hydrocarbon. The above conditions can be applied to hydrogenationHydrotreating conditions in the finishing zone and hydroisomerization conditions in the first catalyst and the second catalyst. Suitable dewaxing conditions and processes are described, for example, in U.S. Pat. nos. 5,135,638, 5,282,958, and 7,282,134.
While the catalyst system and process have been generally described in terms of a combination of a first catalyst composition and a second catalyst composition comprising SSZ-91 and SSZ-95 molecular sieves, it should be understood that additional catalysts (including layered catalysts) and treatment steps may be present, e.g., including one or more hydrotreating catalysts/steps, guard layers, and/or one or more hydrofinishing catalysts/steps.
Examples
SSZ-91 is synthesized according to US 10,618,816, while SSZ-95 is synthesized according to US 10,272,422. Alumina as a catalyst from SasolAlumina and->Alumina or +.>Alumina is provided. The SSZ-91 molecular sieve has a silica to alumina ratio (SAR) of 120 or less.
EXAMPLE 1 preparation of hydroisomerization catalyst
Hydroisomerization catalyst a was prepared as follows: microcrystalline SSZ-91 is combined withThe alumina was composited to provide a mixture containing 65 wt% SSZ-91 zeolite. The mixture is extruded, dried and calcined, and the dried and calcined extrudate is impregnated with a solution containing platinum. The total platinum loading was 0.6 wt%.
EXAMPLE 2 preparation of hydroisomerization catalyst B
Hydroisomerization catalyst B was prepared as described for catalyst a to provide a mixture containing 45 wt% SSZ-95. The dried and calcined extrudate was impregnated with platinum to provide a total platinum loading of 0.325 wt.%.
Example 3 hydroisomerization Property of catalyst A, B and combined A and B System
The Vacuum Gas Oil (VGO) hydrocracked product feedstock having the properties shown in table 1 was hydroisomerized using catalysts a and B.
TABLE 1
Hydroisomerization reactions are carried out in a straight-through microcell fixed bed reactor (without recycle) and only feedstock and hydrogen are fed into the reactor. Run was run at 2300psig total pressure. The raw materials are reacted for 1h -1 Is passed through the reactor. The hydrogen to oil ratio was about 4000scfb and the reactor temperature ranged from 550°f to 650°f. The base oil product is separated from the fuel by a distillation section.
The test was carried out using catalyst a alone, catalyst B alone, a layered catalyst system with catalyst a on top of catalyst B in the same reactor ("a/B"), and a layered catalyst system with catalyst B on top of catalyst a in the same reactor ("B/a"). The layered A/B and B/A catalyst systems were carried out using 50% by volume of catalyst A and 50% by volume of catalyst B. The test of catalyst a alone was used as a "base case" for determining the different hydroisomerization catalyst temperatures. The catalyst hydroisomerization performance results are shown in table 2.
TABLE 2
The layered a/B and B/a catalyst systems showed significantly higher base oil yields of 2 wt.% or higher compared to catalyst a alone (SSZ-91) and catalyst B alone (SSZ-95). In addition, the viscosity index of the layered catalyst system is about 1-2 points higher than that of the single catalyst system.
The foregoing description of one or more embodiments of the invention has been presented for purposes of illustration and description, it is appreciated that variations may be utilized that still incorporate the essence of the invention. Reference should be made to the appended claims in determining the scope of the invention.
All patents and publications cited in the foregoing description of the invention are incorporated herein by reference for the purpose of U.S. patent practice, and in the permitted other patent offices, as long as any information contained therein is consistent with and/or supplements the foregoing disclosure.
Claims (20)
1. A hydroisomerization catalyst system useful for preparing dewaxed products including base oils, said catalyst system comprising
A first catalyst composition comprising an SSZ-91 molecular sieve; and
a second catalyst composition comprising an SSZ-95 molecular sieve;
wherein the first catalyst composition and the second catalyst composition are arranged such that a hydrocarbon feedstock can be contacted with either the first catalyst composition or the second catalyst composition sequentially to provide a first product, followed by contacting the first product with the other catalyst composition to provide a second product.
2. The catalyst system of claim 1, wherein the first catalyst composition and the second catalyst composition are arranged such that the feedstock is fed to the first catalyst composition to form the first product.
3. The catalyst system of claim 1, wherein the first catalyst composition and the second catalyst composition are arranged such that the feedstock is fed to the second catalyst composition to form the first product.
4. The catalyst system of claim 1, wherein the molecular sieve of each of the first and second catalyst compositions is combined with a matrix material to form a first base material and a second base material, respectively, and wherein each of the first and second catalyst compositions further comprises at least one modifier selected from groups 6 to 10 and 14 of the periodic table of elements, and optionally further comprises a group 2 metal of the periodic table of elements.
5. The catalyst system of claim 1, wherein the SSZ-91 molecular sieve comprises a ZSM-48 type zeolite material, the molecular sieve having:
at least 70% polytype 6 of the total ZSM-48 type material;
type EUO phase in an amount between 0% and 3.5% by weight; and
a polycrystalline aggregate morphology comprising crystallites having an average aspect ratio between 1 and 8.
6. The catalyst system of claim 5, wherein the SSZ-91 molecular sieve has a silica to alumina molar ratio in the range of 40 to 220 or 50 to 220 or 40 to 200 or 50 to 140.
7. The catalyst system of claim 5, wherein the SSZ-91 molecular sieve comprises one or more of:
at least 80% or 90% of polytype 6 of the total ZSM-48-type material;
EU-1 between 0.1 wt% and 2 wt%;
crystallites having an average aspect ratio between 1 and 5, or between 1 and 3;
or a combination thereof.
8. The catalyst system of claim 1, wherein the SSZ-95 molecular sieve is an MTT framework molecular sieve having a molar ratio of silica to alumina of 20 to 70, a total micropore volume of between 0.005cc/g and 0.02 cc/g; and H-D exchangeable acid site densities of up to 50% relative to SSZ-32.
9. The catalyst system of claim 4, wherein the modifier is present in an amount of 0.01 wt.% to 5.0 wt.% or 0.01 wt.% to 2.0 wt.% or 0.1 wt.% to 2.0 wt.% (based on total catalyst weight).
10. The catalyst system of claim 4, wherein the catalyst comprises Pt or a combination of Pt and Pd as the modifier, optionally further comprising Mg, in an amount of 0.01 wt% to 1.0 wt%, or 0.3 wt% to 0.8 wt% Pt or a combination of Pt and Pd.
11. The catalyst system of claim 4, wherein the matrix material for one or both of the first catalyst composition and the second catalyst composition is selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, or a combination thereof.
12. The catalyst system of claim 11, wherein one or both of the first catalyst composition and the second catalyst composition comprises 0.01 wt% to 5.0 wt% of the modifier, 0 wt% to 99 wt% of the matrix material, and 0.1 wt% to 99 wt% of the molecular sieve.
13. The catalyst system of claim 1, wherein the second stage product is a base oil product having a viscosity index of at least about 109 and/or a pour point of no greater than about-10 ℃ or-13 ℃, or is used to prepare a base oil product having a viscosity index of at least about 109 and/or a pour point of no greater than about-10 ℃ or-13 ℃.
14. A process for producing a base oil product having increased yield of base oil product, the process comprising contacting a hydrocarbon feedstock with the hydroisomerization catalyst system of claim 1 under hydroisomerization conditions to produce the base oil product.
15. The process of claim 14, wherein the hydrocarbon feedstock comprises a gas oil; vacuum gas oil; residue after long boiling; vacuum residue; atmospheric distillate; a heavy fuel; an oil; waxes and paraffins; used oil; deasphalted residue or crude oil; a charge resulting from a thermal or catalytic conversion process; shale oil; circulating oil; fats, oils and waxes of animal and vegetable origin; petroleum and slack wax; or a combination thereof.
16. The process of claim 14, wherein using the catalyst system of claim 1 increases the base oil yield compared to the same process using only the first catalyst composition or the second catalyst composition.
17. The process of claim 16, wherein using the catalyst system of claim 1 increases the base oil yield by at least about 1 wt% as compared to the same process using only the first catalyst composition or the second catalyst composition.
18. The process of claim 14, wherein the first catalyst composition and the second catalyst composition are arranged such that the hydrocarbon feedstock is fed to the first catalyst composition to form the first product.
19. The process of claim 14, wherein the first catalyst composition and the second catalyst composition are arranged such that the hydrocarbon feedstock is fed to the second catalyst composition to form the first product.
20. The process of claim 14 wherein the second stage product is a base oil product having a viscosity index of at least about 109 and/or a pour point of no greater than about-13 ℃ or-10 ℃, or is used to prepare a base oil product having a viscosity index of at least about 109 and/or a pour point of no greater than about-13 ℃ or-10 ℃.
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| US17/095,337 | 2020-11-11 | ||
| US17/095,337 US20220143588A1 (en) | 2020-11-11 | 2020-11-11 | Catalyst system and process using ssz-91 and ssz-95 |
| PCT/US2021/058893 WO2022103913A1 (en) | 2020-11-11 | 2021-11-11 | Catalyst system and process using ssz-91 and ssz-95 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852207A (en) | 1973-03-26 | 1974-12-03 | Chevron Res | Production of stable lubricating oils by sequential hydrocracking and hydrogenation |
| US4673487A (en) | 1984-11-13 | 1987-06-16 | Chevron Research Company | Hydrogenation of a hydrocrackate using a hydrofinishing catalyst comprising palladium |
| EP0458895B1 (en) | 1989-02-17 | 1995-09-20 | CHEVRON U.S.A. Inc. | Isomerization of waxy lube oils and petroleum waxes using a silicoaluminophosphate molecular sieve catalyst |
| US5282958A (en) | 1990-07-20 | 1994-02-01 | Chevron Research And Technology Company | Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons |
| US6468501B1 (en) | 2000-09-14 | 2002-10-22 | Chevrontexaco Corporation | Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites |
| US7282134B2 (en) | 2003-12-23 | 2007-10-16 | Chevron Usa, Inc. | Process for manufacturing lubricating base oil with high monocycloparaffins and low multicycloparaffins |
| US8182672B2 (en) * | 2007-12-28 | 2012-05-22 | Exxonmobil Research And Engineering Company | Process for preparing lube basestocks having superior low temperature properties at high VI |
| US8298403B2 (en) * | 2008-12-16 | 2012-10-30 | Exxonmobil Research And Engineering Company | Dewaxing catalysts and processes |
| US20150336091A1 (en) * | 2014-05-21 | 2015-11-26 | Chevron U.S.A. Inc. | Molecular sieve ssz-95 |
| DK3145865T3 (en) | 2014-05-21 | 2021-03-08 | Chevron Usa Inc | Methods Using Molecular Sieve SSZ-95 |
| US9573124B2 (en) | 2014-05-21 | 2017-02-21 | Chevron U.S.A. Inc. | Method for making molecular sieve SSZ-95 |
| JP2018531864A (en) | 2015-08-27 | 2018-11-01 | シェブロン ユー．エス．エー． インコーポレイテッド | Molecular sieve SSZ-91, method for preparing SSZ-91, and use of SSZ-91 |
| US9920260B2 (en) * | 2015-08-27 | 2018-03-20 | Chevron U.S.A. Inc. | Processes using molecular sieve SSZ-91 |
| US9802830B2 (en) * | 2015-08-27 | 2017-10-31 | Chevron U.S.A. Inc. | Molecular sieve SSZ-91 |
| CN113891929A (en) * | 2019-05-01 | 2022-01-04 | 雪佛龙美国公司 | Oligomerization and hydroisomerization of base oils produced from NAO over ionic catalysts |
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